US20210253764A1 - High temperature resistant photocurable material for 3d inkjet printing and preparation method thereof, 3d printing product and 3d printer - Google Patents

High temperature resistant photocurable material for 3d inkjet printing and preparation method thereof, 3d printing product and 3d printer Download PDF

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US20210253764A1
US20210253764A1 US17/243,487 US202117243487A US2021253764A1 US 20210253764 A1 US20210253764 A1 US 20210253764A1 US 202117243487 A US202117243487 A US 202117243487A US 2021253764 A1 US2021253764 A1 US 2021253764A1
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reactive
high temperature
methyl
temperature resistant
inkjet printing
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Yinbo Yang
Qiancheng Yang
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Zhuhai Sailner 3D Technology Co Ltd
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Zhuhai Sailner 3D Technology Co Ltd
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    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
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    • C—CHEMISTRY; METALLURGY
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Definitions

  • the present application relates to 3D printing technology, in particular to a high temperature resistant photocurable material for 3D inkjet printing, a preparation method thereof, a 3D printing product and a 3D printer.
  • Existing 3D molding technologies using photocurable materials mainly include: Stereo lithography Appearance (SLA) technology, Digital Light Procession (DLP) technology and 3D inkjet printing technology.
  • SLA Stereo lithography Appearance
  • DLP Digital Light Procession
  • 3D inkjet printing technology 3D inkjet printing technology.
  • a main working principle of the SLA technology is: a photocurable material for three-dimensional molding which contains a liquid photosensitive resin is filled in a resin tank.
  • a liftable worktable is located at a height of a thickness of a section layer below a liquid surface.
  • a focused ultraviolet laser beam scans along the liquid surface in accordance with a requirement of a cross-sectional profile, and the liquid photosensitive resin in a scanned area is cured in an order from dot to line and from line to surface to obtain a resin flake with the cross-sectional profile.
  • the worktable is lift down a height of a layer of flake, and the cured resin flake is covered by a new layer of the liquid photosensitive resin for a second layer of laser scanning and curing, and the newly cured layer is firmly cohered on the previous layer. Repeat in such way until the molding of a whole product is accomplished.
  • DLP printing uses a high-resolution digital light processor projector to illuminate a liquid photosensitive resin. Therefore, the DLP technology also performs photocuring layer by layer.
  • the 3D inkjet printing technology is based on a working principle of an inkjet printer, and to enable, under an excitation of digital signals, liquid (a photocurable material for three-dimensional molding) in a chamber to form droplets in an instant, and the droplets are sprayed out from a nozzle at a certain speed and frequency, and cured and molded layer by layer according to a specified path to finally obtain a 3D object.
  • liquid a photocurable material for three-dimensional molding
  • the 3D inkjet printing technology has a higher requirement on viscosity and fluency of a photocurable material used.
  • a viscosity of the photocurable material needs to be reduced to a viscosity suitable for normal spraying, such as 8-15 cp, especially when the normal operating temperature of the print head is lower than 80° C.
  • the viscosity of the photocurable material is required to be reduced to a viscosity suitable for normal spraying in an instant, which requires the photocurable material has a lower viscosity at a room temperature 25° C., such as less than 100 cp; while the photocurable material with the lower viscosity at the room temperature usually has a lower glass transition temperature Tg, generally 40-60° C., thereby causing that a solid product formed after the photocurable material is irradiated and cured has a low temperature resistance property, and a heat deflection
  • an embodiment of the present disclosure provides a high temperature resistant photocurable material for 3D inkjet printing, which can perform a normal inkjet printing at a lower temperature, and also has excellent high temperature resistance property under a premise of ensuring that a 3D printing product has good mechanical properties, especially has an outstanding impact strength resistance.
  • An embodiment of the present disclosure provides a preparation method of the above-mentioned high temperature resistant photocurable material for 3D inkjet printing, which has characteristics that a preparation process thereof is simple and feasible.
  • An embodiment of the present disclosure provides a 3D printing product. Since the above-mentioned high temperature resistant photocurable material for 3D inkjet printing is used for printing, the 3D printing product has good high temperature resistance property and impact strength resistance.
  • An embodiment of the present disclosure provides a 3D printer whose material storage container contains the above-mentioned high temperature resistant photocurable material for 3D inkjet printing, so that it has advantages of good printing fluency, low print head operating temperature, and the obtained 3D printing product has outstanding impact strength resistance and high temperature resistance property.
  • an embodiment of the present disclosure provides a high temperature resistant photocurable material for 3D inkjet printing, including the following components: 60-99 parts by weight of first vinyl compounds, 0-39 parts by weight of second vinyl compounds, and 0.5-4 parts by weight of free radical photoinitiators, where:
  • the first vinyl compounds have a non-reactive cyclic structure, and the non-reactive cyclic structure does not have photopolymerization properties under initiations of the free radical photoinitiators;
  • the second vinyl compounds do not have the aforementioned non-reactive cyclic structure, and the number of methylene “—CH2-” on a main chain of the second vinyl compounds is not less than 3.
  • the high temperature resistant photocurable material for 3D inkjet printing provided by the embodiment of the present disclosure, on one hand, enhances the mechanical properties of the photocurable material, especially the impact strength resistance property, by selecting the vinyl compounds without the non-reactive cyclic structure and the number of methylene “—CH2-” groups on the main chain of which is not less than 3, that is, greater than or equal to 3; on the other hand, may effectively reduce a moving or swing phenomenon of a main chain segment of a molecule at a high temperature by selecting the vinyl compounds with the non-reactive cyclic structure, so that a degree of dimensional deformation of a photocuring object under load is small in a high temperature environment, and degrees of degradation of the mechanical properties are relatively low, thereby increasing a temperature that the photocurable material could withstand under specified degrees of deformation and mechanical properties influence, that is, a thermal deformation temperature of the photocurable material is increased.
  • the embodiment of the present disclosure makes the finally 3D printing product obtained by 3D inkjet printing of the prepared photocurable material have outstanding high temperature resistance property and excellent mechanical properties, especially have outstanding impact resistance by combining the above-mentioned first vinyl compounds with the non-reactive cyclic structure and the second vinyl compounds without the non-reactive cyclic structure and the number of “—CH2-” groups on the main chain of which is greater than or equal to 3.
  • the number of methylene on a main chain of at least partial of the first vinyl compounds is not less than 3. That is, in the first vinyl compounds, partial or all components are vinyl compounds with the non-reactive cyclic structure and containing 3 or more “—CH2-” groups on the main chain.
  • the high temperature resistant photocurable material for 3D inkjet printing contains the above first vinyl compounds the number of “—CH2-” groups on the main chain of which is greater than or equal to 3, especially when the content of the first vinyl compounds the number of methylene on the main chain of which is not less than 3 is 9-39 parts by weight, the 3D printing product obtained by 3D inkjet printing of the photocurable material may have higher temperature resistance property, and also have good mechanical properties, especially that the impact strength resistance has been significantly improved.
  • non-reactive means that, under the current conventional conditions of 3D inkjet printing, a free radical polymerization reaction would not occur under initiation of free radical photoinitiators.
  • non-reactive cyclic structure refers to a cyclic structure groups that does not participate in free radical polymerization reactions in 3D inkjet printing processes.
  • An exemplary non-reactive cyclic structure may be, for example, non-reactive aliphatic ring such as saturated aliphatic ring, non-reactive aromatic ring, and non-reactive N, O, S-containing heterocyclic ring, and the like.
  • the above-mentioned non-reactive cyclic structure may have substituents or no substituents.
  • the above-mentioned first vinyl compounds may be one or more vinyl monomers with the non-reactive cyclic structure, may also be one or more vinyl oligomers with the non-reactive cyclic structure, and may also be a mixture of one or more vinyl monomers with the non-reactive cyclic structure and one or more vinyl oligomers with the non-reactive cyclic structure.
  • the above-mentioned first vinyl compounds at least include a vinyl compound with a non-reactive nitrogen-containing heterocyclic ring.
  • the above-mentioned non-reactive nitrogen-containing heterocyclic ring is not specifically limited by the embodiment of the present disclosure, as long as it does not have the photopolymerization property under an initiation of a free radical photoinitiator, such as morpholine, 2-pyrrolidone, caprolactam, and the like.
  • the high temperature resistant photocurable material for 3D inkjet printing contains at least one vinyl compound with the non-reactive nitrogen-containing heterocyclic ring, which can further improve the high temperature resistance property of the 3D printing product.
  • the aforementioned vinyl compound with the non-reactive nitrogen-containing heterocyclic ring includes: at least one of a (methyl)acrylate monomer with a non-reactive nitrogen-containing heterocyclic ring, a (methyl)acrylate oligomer with a non-reactive nitrogen-containing heterocyclic ring, an amide monomer with a non-reactive nitrogen-containing heterocyclic ring, and the like.
  • the (methyl)acrylate monomer with the non-reactive nitrogen-containing heterocyclic ring may be, for example, M370 produced by Goody Company, EM2308 produced by Changxing Company, PAR-68A produced by Shenzhen Sabis Company, and A9300-1CL produced by Xinzhongcun Company, and the like;
  • the (methyl)acrylate oligomer with the non-reactive nitrogen-containing heterocyclic ring may be, for example, BMA-200, XMA-222LF, and the like, produced by Bomar;
  • the amide monomer with the non-reactive nitrogen-containing heterocyclic ring may be, for example, acryloylmorpholine (ACMO), N-vinylpyrrolidone, N-vinylcaprolactam, and the like.
  • the vinyl compound with the non-reactive nitrogen-containing heterocyclic ring is preferably more than 10 parts by weight, for example, 10-50 parts by weight.
  • the first vinyl compounds preferably include 10-50 parts by weight of vinyl monomers with a non-reactive nitrogen-containing heterocyclic structure, for example, may include 10-50 parts by weight of the (methyl)acrylate monomer with the non-reactive nitrogen-containing heterocyclic ring, or may include 10-50 parts by weight of the amide monomer with the non-reactive nitrogen-containing heterocyclic ring, and may also simultaneously include the acrylate monomer with the non-reactive nitrogen-containing heterocyclic ring and the amide monomer with the non-reactive nitrogen-containing heterocyclic ring, and the total mass of the two is 10-50 parts by weight.
  • the first vinyl compounds preferably include a vinyl compound with a non-reactive nitrogen-containing heterocyclic ring, and a vinyl compound with a non-reactive cyclic structure and the number of methylene on a main chain of which is greater than or equal to 3, and the two are different compounds.
  • the vinyl compound with the non-reactive cyclic structure and the number of methylene on the main chain of which is greater than or equal to 3 is 9-39 parts by weight.
  • the first vinyl compounds may also include at least one of the following four vinyl compounds:
  • a vinyl compound with a non-reactive aliphatic ring a vinyl compound with a non-reactive aromatic ring, a vinyl compound with a non-reactive oxygen-containing heterocyclic ring, and a vinyl compound with a non-reactive sulfur-containing heterocyclic ring.
  • each of the above four vinyl compounds does not exceed 50 parts by weight.
  • this non-reactive aliphatic ring is a non-reactive cyclic structure, and this non-reactive aliphatic ring may be a monocyclic or polycyclic (condensed ring) structure.
  • the vinyl compound with the non-reactive aliphatic ring may be one or more (methyl)acrylate monomers with a non-reactive aliphatic ring, may also be one or more (methyl)acrylate oligomers with a non-reactive aliphatic ring, and may also be a mixture of one or more (methyl)acrylate monomers with the non-reactive aliphatic ring and one or more (methyl)acrylate oligomers with the non-reactive aliphatic ring.
  • the (methyl)acrylate monomers with the non-reactive aliphatic ring may be, for example, at least one of dicyclopentadiene methacrylate, dicyclopentyl (methyl)acrylate, isobornyl (methyl)acrylate, 1-adamantane (methyl)acrylate, cyclohexane dimethanol diacrylate, tricyclodecane dimethanol di(methyl)acrylate, and the like; and the (methyl)acrylate oligomers with the non-reactive aliphatic ring include at least one of aliphatic polyurethane acrylate, aliphatic epoxy acrylate, and the like.
  • this non-reactive aromatic ring is a non-reactive cyclic structure.
  • the vinyl compound with the non-reactive aromatic ring may be one or more (methyl)acrylate monomers with a non-reactive aromatic ring, may also be one or more (methyl)acrylate oligomers with a non-reactive aromatic ring, and may also be a mixture of one or more (methyl)acrylate monomers with the non-reactive aromatic ring and one or more (methyl)acrylate oligomers with the non-reactive aromatic ring.
  • the (methyl)acrylate monomers with the non-reactive aromatic ring are selected from at least one of ethoxylated bisphenol A di(methyl)acrylate, propoxylated bisphenol A di(methyl)acrylate, benzyl methacrylate, 2-phenoxyethyl methacrylate, and the like;
  • the (methyl)acrylate oligomers with the non-reactive aromatic ring are selected from at least one of bisphenol A (methyl)epoxy acrylate, aromatic polyurethane (methyl)acrylate, aromatic polyester (methyl)acrylate, and the like.
  • the (methyl)acrylate monomers with the non-reactive aromatic ring and the number of “—CH2-” groups on a main chain of which is greater than or equal to 3 include ethoxylated bisphenol A di(methyl)acrylate, propoxylated bisphenol A di(methyl)acrylate, and the like; the (methyl)acrylate monomers with the non-reactive aromatic ring and the number of “—CH2-” groups on a main chain of which is less than 3 include benzyl methacrylate, 2-phenoxyethyl methacrylate, and the like; the (methyl)acrylate oligomers with the non-reactive aromatic ring and the number of “—CH2-” groups on a main chain of which is greater than or equal to 3 include bisphenol A (methyl)epoxy acrylate, aromatic polyurethane (methyl)acrylate, aromatic polyester (methyl)acrylate, and the like
  • the vinyl compound with the non-reactive oxygen(sulfur)-containing heterocyclic ring may be at least one of a (methyl)acrylate monomer with a non-reactive oxygen(sulfur)-containing heterocyclic structure, and a (methyl)acrylate oligomer with a non-reactive oxygen(sulfur)-containing heterocyclic structure.
  • the (methyl)acrylate monomer with the non-reactive oxygen(sulfur)-containing heterocyclic structure and the number of “—CH2-” groups on a main chain of which is greater than or equal to 3 may be oxyheterocyclic ethane diacrylate, trimethylolpropane formal acrylate, and the like.
  • they may also contain nitrogen atoms at the same time, such as acryloyl morpholine, and the heterocyclic structure contains both O and N.
  • glass transition temperatures Tg of the first vinyl compounds are preferably not lower than 20 ° C., so as to further ensure the high temperature resistance property of the obtained high temperature resistant photocurable material for 3D inkjet printing.
  • the second vinyl compounds may be one or more (methyl)acrylate monomers without a non-reactive cyclic structure and the number of methylene on a main chain of which is not less than 3, may also be one or more (methyl)acrylate oligomers without a non-reactive cyclic structure and the number of methylene on a main chain of which is not less than 3, and may also be a mixture of one or more(methyl)acrylate monomers without the non-reactive cyclic structure and the number of the methylene on the main chain of which is not less than 3 and one or more (methyl)acrylate oligomers without the non-reactive cyclic structure and the number of the methylene on the main chain of which is not less than 3.
  • the above-mentioned (methyl)acrylate monomers without the non-reactive cyclic structure and the number of the methylene on the main chain of which is not less than 3 may be, for example, at least one of 3-hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2-dimethyl propyl ester diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, and the like;
  • the above-mentioned (methyl)acrylate oligomers without the non-reactive cyclic structure and the number of the methylene on the main chain of which is not less than 3 may be, for example, at least one of polyether acrylate, polyester acrylate, hyperbranched acrylate oligomer, and the like.
  • a total content of the vinyl oligomers with the non-reactive cyclic structure and the (methyl)acrylate oligomers without the non-reactive cyclic structure and the number of “—CH2-” groups on the main chain of which is greater than or equal to 3 are less than or equal to 40 parts by weight.
  • glass transition temperatures of the second vinyl compounds are preferably not lower than 60° C. to ensure the high temperature resistance property of the 3D printing product.
  • the free radical photoinitiators used in the embodiments of the present disclosure are preferably free radical ultraviolet photoinitiators.
  • the embodiments of the present disclosure do not specifically limit types of the free radical ultraviolet photoinitiators, as long as free radicals are generated under ultraviolet light irradiation to enable a polymerization reaction of the first vinyl compounds and the second vinyl compounds.
  • a dosage of the radical ultraviolet photoinitiators may be reasonably determined according to initiation efficiency thereof and the actual conditions of the first vinyl compounds and the second vinyl compounds.
  • the free radical ultraviolet photoinitiators in the embodiments of the present disclosure may be a hydrogen abstraction type free radical photoinitiator and/or a cleavage type free radical photoinitiator.
  • the hydrogen abstraction type free radical photoinitiator is selected from one or more of benzophenone/tertiary amines and thioxanthone/tertiary amines; and the cleavage type free radical photoinitiator is selected from one or more of ⁇ -hydroxyketones, ⁇ -amino ketones, acyl phosphine oxides and oxime esters.
  • the thioxanthone is preferably ITX (isopropyl thioxanthone), and the tertiary amines co-initiator at least contains one ⁇ -H in a molecular structure as a hydrogen donor of the hydrogen abstraction type free radical photoinitiator.
  • ITX isopropyl thioxanthone
  • tertiary amines co-initiator at least contains one ⁇ -H in a molecular structure as a hydrogen donor of the hydrogen abstraction type free radical photoinitiator.
  • tertiary amines co-initiators for example, may be tertiary amine benzoate, active amine, and the like.
  • the tertiary amine benzoate includes N,N-dimethyl ethyl benzoate, N,N-dimethyl benzoic acid-2-ethylhexyl ester, dimethylaminoethyl benzoate, and the like;
  • the active amine is a tertiary amine with an acryloxy group that can participate in a cross-linking reaction, such as reactive tertiary amine co-initiator 6420 from Changxing, Genomer 5142 from RAHN, and EBECRYL 7100 from Cytec.
  • cleavage free radical photoinitiator may be an ⁇ -hydroxyketone photoinitiator, such as products like 1173 (2-hydroxy-2-methyl-1-phenylacetone), 184 (1-hydroxy-cyclohexyl phenyl ketone), 2959 (2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenylacetone), and the like; may also be an ⁇ -amino ketone, such as products like 907 (2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone), 369 (2-benzyl-2-dimethylamino-1-(4-morpholinphenyl)-1-butanone); and may also be an acyl phosphine oxide, such as products like a trade name of TEPO (2,4,6-trimethylbenzoyl-ethoxy-phenyl phosphine oxide), TPO (2,4,6-trimethylbenzoyl-diphenyl phosphine
  • TEPO
  • the first vinyl compounds are 60-99 parts by weight
  • the second vinyl compounds are 0-39 parts by weight
  • the free radical photoinitiators are 0.5-4 parts by weight.
  • the high temperature resistant photocurable material for 3D inkjet printing provided by the embodiments of the present disclosure may further include 0.01 to 5 parts by weight of auxiliary agents.
  • the embodiments of the present disclosure do not specifically limit types of the auxiliary agents, and suitable auxiliary agents may be selected according to actual conditions to improve the quality of 3D inkjet printing and obtain high-quality printing products.
  • auxiliary agents used may be selected from at least one of surfactants, defoamers and polymerization inhibitors, and may also include other types of auxiliary agents.
  • the embodiments of the present disclosure have no special restrictions on the surfactants, as long as they can reduce the surface tension of the high temperature resistant photocurable material for 3D inkjet printing and are beneficial to improve the levelling property of materials.
  • Currently available surfactants on the market include modified polysiloxane polymer surfactants BYK-333, BYK-337, BYK-371, BYK-377, BYK1798, BYK-UV3530, BYK-UV3575, and the like from BYK company, modified polysiloxane polymer surfactants Tego wet 270, TEGO wet 500, Tego Glide 450, TEGO RAD 2010, TEGO RAD 2011, and the like from Tego company.
  • the defoamers are mainly used to suppress or eliminate bubbles generated during a preparation process and a printing process of the high temperature resistant photocurable material for 3D inkjet printing, so as to prevent the generated bubbles from affecting the fluency of the high temperature resistant photocurable material in the printing process.
  • the defoamers that can be used in the embodiments of the present disclosure are for example organic silicon polymer defoamers BYK-088, BYK020, and the like from BYK company, modified polysiloxane copolymer BYK-1798 and the like, defoamers without organic silicon BYK055 and the like, non-organic silicon defoamers TEGO Airex 920, TEGO Airex 921 from Tego and the like.
  • the polymerization inhibitors are mainly used to prevent polymerization reactions of free radicals in the high temperature resistant photocurable material composition for 3D inkjet printing, improve the storage stability of the high temperature resistant photocurable material, and prevent the photocurable material composition from chemical reactions and occurring coagulation phenomenons.
  • the specific selection of the polymerization inhibitors in the embodiments of the present disclosure is not particularly limited, as long as a polymerization inhibitor that can improve the storage stability of the high temperature resistant photocurable material and has no effect on occurrence of a photocurable reaction during a 3D printing process.
  • Commonly used polymerization inhibitors may be, for example, GENORAD 16, GENORAD 18, GENORAD 20, GENORAD 22, and the like from RAHN company, Tinuvin234, Tinuvin770, Irganox245 from BASF, Cytec S100, Cytec 130, and the like, and Irgastab UV10, Irgastab UV 22 and the like from Ciba.
  • the high temperature resistant photocurable material for 3D inkjet printing may further include 0-10 parts by weight of colorants.
  • the high temperature resistant photocurable material for 3D inkjet printing is colorless and transparent or basically colorless and transparent.
  • colors and additive amounts of the colorants may be reasonably selected according to actual requirements for the 3D printing product, such as adding pastes in white, red, yellow, blue, black and other color.
  • a self-dispersing nano-scale pigment color paste may be selected, and a surface of the self-dispersing nano-scale pigment color paste has been chemically modified, so that it can prevent the pigment from flocculation and coagulation, thereby ensuring the stability of the high temperature resistant photocurable material for 3D inkjet printing.
  • the self-dispersing nano-scale pigment color paste used is specifically a self-dispersing nano-scale inorganic pigment color paste or a self-dispersing nano-scale organic pigment color paste
  • the self-dispersing nano-scale inorganic pigment color paste may be a white pigment color paste, such as titanium dioxide, zinc oxide, lithopone, lead white, and the like, and may also be a black pigment color paste, such as carbon black, graphite, iron oxide black, aniline black, and the like
  • the self-dispersing nano-scale organic pigment color paste may be a color pigment color paste, such as Golden Red (PR21), Lithol Scarlet (PR49:1), Pigment Red G (PR37), Pigment Red 171 (PR171), Light Fast Yellow G (PY1), Hansa Yellow R (PY10), Permanent Yellow GR (PY13), Pigment Yellow 129 (PY129), Pigment Yellow 150 (PY150), Pigment Yellow 185 (PY185), Phthalocyanine Blue
  • the high temperature resistant photocurable material for 3D inkjet printing provided in some examples of the present disclosure has a viscosity of 10-80 cp, a surface tension of 20-35 mN/m at 25° C.; and a viscosity of 8-15 cp, a surface tension of 20-35 mN/m at an operating temperature, where the operating temperature is at least one temperature of 30-70° C. Therefore, the photocurable material has the viscosity and surface tension suitable for spraying of the print head, which not only facilitates the smooth progress of 3D printing, but also saves energy consumption and effectively prolongs the service life of the print head.
  • An embodiment of the present disclosure also provides a preparation method of the above-mentioned high temperature resistant photocurable material for 3D inkjet printing, including:
  • the above-mentioned filtering of the second mixture may be carried out in a manner of multiple filtering, in particular, may be in a manner of filtering step by step.
  • microporous filter membranes may be used to filter the second mixture at least twice; where a pore diameter of a microporous filter membrane used in a previous filtration is larger than a pore diameter of a microporous filter membrane used in a subsequent filtration, and a pore diameter of a microporous filter membrane used in the last filtration is smaller than a pore diameter of a nozzle of a print head in a 3D inkjet printer, which ensures that the obtained high temperature resistant photocurable material for 3D inkjet printing has good printing fluency and avoids clogging the nozzle of the print head.
  • the second mixture is processed using a manner of two-stage filtration, where a primary filtration adopts a glass fiber membrane with a pore diameter of 0.6 ⁇ m, and a secondary filtration adopts a polypropylene membrane with a pore diameter of 0.2 ⁇ m.
  • a degassing process may also be performed on the collected filtrate. By performing the degassing process on the filtrate, it further ensures that the material has excellent fluency during use, and avoids the interference of bubbles in the material from causing print disconnection, which in turn affects the molding accuracy of the 3D printing product.
  • an operation manner of the degassing process may be reduced pressure degassing, normal pressure degassing or heating degassing, and may also select any two or more degassing manners.
  • a time of the degassing process is controlled to not exceed 5 hours.
  • a degassing time is generally controlled to 1-3 hours.
  • the preparation of the high temperature resistant photocurable material for 3D inkjet printing of the embodiment of the present disclosure needs to be carried out in an environment outside an initiation wavelength range of the selected free radical photoinitiator, so as to avoid that light in the environment induces components in the photocurable material to undergo a polymerization reaction.
  • An embodiment of the present disclosure also provides a 3D printing product, which is obtained using the above-mentioned high temperature resistant photocurable material for 3D inkjet printing by 3D printing.
  • the 3D printing product provided by the embodiment of the present disclosure has outstanding high temperature resistance property and is not easily deformed at high temperatures.
  • the above-mentioned high temperature resistant photocurable material for 3D inkjet printing has good stability, a nozzle of a print head will not be clogged during a printing process, and the printing fluency is good, thus a high-precision 3D printing product could be obtained. Furthermore, using this high temperature resistant photocurable material for 3D inkjet printing also enables the 3D printing product to have advantages of low print shrinkage, excellent mechanical property, especially high impact strength resistant, which further ensures the quality of the 3D printing product.
  • An embodiment of the present disclosure also provides a 3D printer, including an inkjet print head, a material storage container, a connecting device for connecting the inkjet print head and the material storage container, and a bearing platform, where the material storage container contains the above high temperature resistant photocurable material for 3D inkjet printing.
  • the number of the aforementioned material storage container may be set according to the type of the high temperature resistant photocurable material, which is not particularly limited by the embodiment of the present disclosure herein.
  • the above-mentioned connecting device may specifically be a connecting pipe or connecting devices in other forms, as long as the above-mentioned functions can be realized.
  • the inkjet print head may specifically be a single-channel print head or a multi-channel print head, and may also be a combination of a single-channel print head and a multi-channel print head.
  • the above-mentioned 3D printer may further include a controller that is capable of controlling the material storage container to supply ink to the inkjet print head, that is, through this controller, the high temperature resistance photocurable material for 3D inkjet printing contained in the material storage container is supplied to the inkjet print head via the connecting device, and finally sprayed out from the nozzle of the inkjet print head to realize printing.
  • a controller that is capable of controlling the material storage container to supply ink to the inkjet print head, that is, through this controller, the high temperature resistance photocurable material for 3D inkjet printing contained in the material storage container is supplied to the inkjet print head via the connecting device, and finally sprayed out from the nozzle of the inkjet print head to realize printing.
  • the above-mentioned 3D printer may also include an ultraviolet light source, and this ultraviolet light source may specifically be an ultraviolet light emitting diode.
  • the ultraviolet light source may be controlled by the controller, so that the ultraviolet light source irradiates a layer formed by the high temperature resistant photocurable material for 3D inkjet printing on the bearing platform to realize a photocuring molding.
  • the high temperature resistant photocurable material for 3D inkjet printing provided by the embodiments of the present disclosure has the following advantages.
  • the high temperature resistance property and the mechanical properties of the photocurable material can be effectively improved by rationally selecting the first vinyl compounds with the non-reactive cyclic structure and the second vinyl compounds with greater than or equal to 3 of “—CH2-” groups on the main chain; especially, when partial of the first vinyl compounds have a nitrogen-containing heterocyclic structure, the high temperature resistance property of the photocurable material can be further improved.
  • This photocurable material has a low viscosity at a room temperature, and has a viscosity of 8-15 cp and a surface tension of 20-35 mN/m at at least one operating temperature of 30-70° C. Therefore, performing normal inkjet printing at a lower operating temperature of 30-70° C. can be achieved, and the printed product has high temperature resistance property and excellent mechanical properties; at the same time, since the normal inkjet printing can be done at low temperatures, energy is effectively saved, and the service life of the print head is prolonged.
  • the 3D printing product printed with this photocurable material has high accuracy, a size error of a printed model is less than 0.1 mm, a heat deflection temperature (0.45 MPa) is higher than 80° C., the tensile strength is higher than 80 MPa, the bending strength is higher than 120 Mpa, and the impact strength resistance is higher than 10 J/m, and the Shore hardness is higher than 80D, thus the 3D printing product has good mechanical properties and meets requirements of actual usage.
  • the preparation method of the high temperature resistant photocurable material for 3D inkjet printing provided by the embodiment of the present disclosure has the characteristics of simple and feasible configuration process, which is convenient for actual production, application and promotion.
  • the 3D printing product provided by the embodiment of the present disclosure uses the above-mentioned high temperature resistant photocurable material for 3D inkjet printing as a raw material, so it has outstanding high temperature resistance property, good mechanical properties, higher accuracy and lower shrinkage. Therefore, the 3D printing product has good quality.
  • the material storage container thereof contains the above-mentioned high temperature resistant photocurable material for 3D inkjet printing, which has good fluency during the printing process, and the nozzle of the print head is not easily clogged, and the like, and can work smoothly at a lower temperature (such as 30-70° C.), which not only enables the 3D printer to have good usage performance and long service life, but also to obtain high-quality 3D printing product.
  • a lower temperature such as 30-70° C.
  • FIG. 1 is a schematic structural diagram of a 3D printer provided in Embodiment 7 of the present disclosure.
  • This embodiment provides a high temperature resistant photocurable material for 3D inkjet printing, which has the following composition as in Table 1:
  • the preparation method of the high temperature resistant photocurable material for 3D inkjet printing is as follows:
  • This embodiment provides a high temperature resistant photocurable material for 3D inkjet printing, which has the following composition as in Table 2:
  • the preparation method of the high temperature resistant photocurable material for 3D inkjet printing in this embodiment is basically the same as that in Embodiment 1, except that the components used are replaced accordingly, and a manner of heating and degassing is used in step (3), the filtrate obtained in step (2) is heated to 40° C. for performing a degassing process, and a degassing time is 50 min.
  • the high temperature resistant photocurable material for 3D inkjet printing obtained in this embodiment is a transparent material.
  • This embodiment provides a high temperature resistant photocurable material for 3D inkjet printing, which has the following composition as in Table 3:
  • the preparation method of the high temperature resistant photocurable material for 3D inkjet printing in this embodiment is basically the same as that in Embodiment 1, except that the components used are replaced accordingly, and in step (3), the specific time for degassing under reduced pressure is adjusted to 2 hours.
  • the high temperature resistant photocurable material for 3D inkjet printing obtained in this embodiment is a red material.
  • This embodiment provides a high temperature resistant photocurable material for 3D inkjet printing, which has the following composition as in Table 4:
  • the preparation method of the high temperature resistant photocurable material for 3D inkjet printing in this embodiment is basically the same as that in Embodiment 1, except that the components used are replaced accordingly, and normal pressure static degassing is adopted for the degassing process in step (3), a static time is 3 hours.
  • the high temperature resistant photocurable material for 3D inkjet printing obtained in this embodiment is a transparent material.
  • This embodiment provides a high temperature resistant photocurable material for 3D inkjet printing, which has the following composition as in Table 5:
  • Composition of the high temperature resistant photocurable material for 3D inkjet printing in Embodiment 5 Composition Compound/Trade name Weight First vinyl Acryloyl morpholine 20 g compounds Isobornyl acrylate 21.6 g 1-adamantane acrylate 25 g Tricyclodecane dimethanol diacrylate 20 g Ethoxylated bisphenol A dimethylacrylate 10 g Free radical ITX 1 g photoinitiators N,N-dimethyl ethyl benzoate 2 g Auxiliary agents GENORAD 22 (Polymerization inhibitor) 0.2 g TEGO wet 500 (Surfactant) 0.2 g
  • the preparation method of the high temperature resistant photocurable material for 3D inkjet printing in this embodiment is basically the same as that in Embodiment 1, except that the components used are replaced accordingly, and a manner of heating and degassing is used in step (3), the filtrate obtained in step (2) is heated to 50° C. for performing a degassing process, and a degassing time is 30 min.
  • the high temperature resistant photocurable material for 3D inkjet printing obtained in this embodiment is a transparent material.
  • This embodiment provides a high temperature resistant photocurable material for 3D inkjet printing, which has the following composition as in Table 6:
  • composition Compound/Trade name Weight First vinyl Isobornyl acrylate 22.53 g compounds Tricyclodecane dimethanol diacrylate 5 g Aliphatic epoxy acrylate 17 g Trimethylolpropane formal acrylate 30 g Secon 3-hydroxy-2,2-dimethylpropyl-3-hydroxy- 20 g vinyl compounds 2,2-dimethyl propyl ester diacrylate Free radical TPO 3 g photoinitiators Auxiliary agents GENORAD 20 (Polymerization inhibitor) 0.4 g BYK333 (Surfactant) 0.02 g TEGO Airex 920 (Defoamer) 0.05 g Colorants Greenish blue 9S1494 2 g
  • the preparation method of the high temperature resistant photocurable material for 3D inkjet printing in this embodiment is basically the same as that in Embodiment 1, except that the components used are replaced accordingly.
  • the high temperature resistant photocurable material for 3D inkjet printing obtained in this embodiment is blue.
  • This comparative example provides a photocurable material for 3D inkjet printing, which has the following composition as in Table 7:
  • the preparation method of the high temperature resistant photocurable material for 3D inkjet printing in this comparative embodiment 1 is basically the same as that in Embodiment 1, except that the components used are replaced accordingly.
  • the high temperature resistant photocurable material for 3D inkjet printing in this comparative embodiment 1 is red.
  • a DV-I digital viscometer is used to test the viscosity of the photocurable material.
  • the photocurable material is applied to a Sailner J501 3D photocuring inkjet printer, a nozzle temperature is set at 30-70° C., and a model with a length, width, and height of 100 mm ⁇ 100 mm ⁇ 100 mm is printed. After the printing is completed, the actual length, width, and height sizes of the model are tested, the actual length, width, and height sizes are respectively subtracted by 100 mm, and a maximum value of the three difference values is an accuracy size error.
  • the photocurable material is applied to a Sailner J501 3D photocuring inkjet printer, and a tested material of size and specifications required by GB/T2411-2008 “Plastics and ebonite-Determination of indentation hardness by means of a durometer (shore hardness)”, and the shore hardness is tested according to this standard.
  • the photocurable material is applied to a Sailner J501 3D photocurable inkjet printer, a tested material of size and specifications required by GB/T 528-2009 “Rubber, vulcanized or thermoplastic-Determination of tensile stress-strain properties” is printed, and the tensile strength of the high temperature photocurable material of this embodiment is tested according to GB/T1040-2006 “Plastics-Determination of tensile property-Part 1: General principles”.
  • the photocurable material is applied to a Sailner J501 3D photocuring inkjet printer, a tested material of size and specifications required by GB/T 9341-2008 “Plastic-Determination of flexural properties” is printed, and the flexural strength is tested according to this standard.
  • the photocurable material is applied to a Sailner J501 3D photocuring inkjet printer, a tested material of size and specifications required by GB/T 1843-2008 “Plastic-Determination of izod impact strength” is printed, and the impact strength is tested according to this standard.
  • the material composition of this embodiment is applied to a Sailner J501 3D photocuring inkjet printer, a tested material of size and specifications required by GB/T 1634.2-2004 “Plastics-Deformation of temperature of deflection under load-Part 2: Plastics, ebonite and long-fiber-reinforced composites” is printed, and the heat deflection temperature is measured according to this standard (0.45 MPa).
  • the high temperature resistant photocurable material for 3D inkjet printing provided by the embodiments of the present disclosure has a viscosity of 10-80 cp and a surface tension of 20-35 mN/m at room temperature (25° C.); and has a viscosity of 8-15 cp and a surface tension of 20-35 mN/m at least one operating temperature of 30-70° C., therefore, a normal inkjet printing can be performed at a low temperature of 30-70° C., which effectively saves energy and prolongs the service life of the print head.
  • the 3D printing product obtained using the high temperature resistant photocurable material for 3D inkjet printing provided by the embodiments of the present disclosure by 3D inkjet printing has the following properties:
  • a size error of a printed model is less than 0.1 mm, and thus the 3D printing product has very high molding accuracy
  • the heat deflection temperature (0.45 MPa) is higher than 80° C., especially when the content of the vinyl compound with the non-reactive nitrogen-containing heterocyclic is greater than 10 parts by weight (Embodiments 1-5), the heat deflection temperature is higher than 95° C., and thus the 3D printing product has very outstanding temperature resistance;
  • the 3D printing product has good mechanical properties, especially outstanding impact strength resistance, which meets requirements of actual usage.
  • FIG. 1 This embodiment provides a 3D inkjet printer, a schematic diagram thereof is shown in FIG. 1 , which includes a material storage container 1 , an inkjet print head 2 , a connecting device 3 , and a bearing platform 7 , among them:
  • the material storage container 1 contains the high temperature resistant photocurable material for 3D inkjet printing provided in any one of Embodiments 1-6;
  • the connecting device 3 is configured to connect the material storage container 1 and the inkjet print head 2 , and the high temperature resistant photocurable material for 3D inkjet printing contained in the material storage container 1 is supplied to the inkjet print head 2 through the connecting device 3 ;
  • the high temperature resistant photocurable material for 3D inkjet printing sprayed out from the inkjet print head 2 is cured on the bearing platform 7 to form a photocuring layer 6 .
  • the number of the material storage container 1 is not particularly limited by this embodiment, and a corresponding number of the material storage container 1 may be provided according to the type of the high temperature resistant photocurable material for 3D inkjet printing.
  • the above-mentioned connecting device 3 may specifically be a connecting pipe or connecting devices in other forms, as long as it can realize the above-mentioned connection and ink transfer functions.
  • the inkjet print head 2 may specifically be a single-channel print head or a multi-channel print head, or a combination of a single-channel print head and a multi-channel print head.
  • the 3D inkjet printer may further include: a controller 4 and an ultraviolet light source 5 .
  • the controller 4 is capable of controlling the material storage container 1 to supply the high temperature resistant photocurable material to the inkjet print head 2
  • the controller 4 is also capable of controlling the ultraviolet light source 5 to perform ultraviolet radiation and curing for the high temperature resistant photocurable material for 3D inkjet printing sprayed on the bearing platform 7 to form the photocuring layer 6
  • the specific ultraviolet light source 5 may be an ultraviolet light emitting diode.
  • This embodiment provides a 3D printing product, which is obtained using the high temperature resistant photocurable material for 3D inkjet printing in each of the foregoing Embodiments 1-6 by 3D inkjet printing.
  • 3D inkjet printing products in different colors and with high temperature resistance and good mechanical properties can be printed according to requirements, for example, applying the materials in the above Embodiments 1-6 to the Sailner J501 printer or the 3D printer provided by the above Embodiment 7 can respectively print 3D printing products that match colors of the high temperature resistant photocurable material for 3D inkjet printing, and the obtained 3D printing products have an outstanding high temperature resistance property and good mechanical properties.
  • the materials in the above embodiments can also be mixed in a certain proportion to obtain 3D printing products with good high temperature resistance and mechanical properties in other colors.

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CN201811403620.4A CN109593168B (zh) 2018-11-23 2018-11-23 3d喷墨打印用耐高温光固化材料及其制备方法、3d打印制品及3d打印机
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PCT/CN2019/089746 WO2020103421A1 (zh) 2018-11-23 2019-06-03 3d喷墨打印用耐高温光固化材料及其制备方法、3d打印制品及3d打印机

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